CN102718951B - Preparation technologies of double-acid-single-alcohol copolymerization modification PET-A and unidirectional heat shrinkable film thereof - Google Patents
Preparation technologies of double-acid-single-alcohol copolymerization modification PET-A and unidirectional heat shrinkable film thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000005516 engineering process Methods 0.000 title claims abstract description 30
- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 25
- 230000004048 modification Effects 0.000 title claims abstract description 22
- 238000012986 modification Methods 0.000 title claims abstract description 22
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 229920000728 polyester Polymers 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005886 esterification reaction Methods 0.000 claims description 20
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- 230000032050 esterification Effects 0.000 claims description 16
- 238000012856 packing Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 10
- 229940069446 magnesium acetate Drugs 0.000 claims description 10
- 235000011285 magnesium acetate Nutrition 0.000 claims description 10
- 239000011654 magnesium acetate Substances 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 10
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010009 beating Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- GAPFINWZKMCSBG-UHFFFAOYSA-N 2-(2-sulfanylethyl)guanidine Chemical compound NC(=N)NCCS GAPFINWZKMCSBG-UHFFFAOYSA-N 0.000 claims 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract description 8
- 235000013305 food Nutrition 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- 230000007096 poisonous effect Effects 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 2
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920006300 shrink film Polymers 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 230000002457 bidirectional effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- Engineering & Computer Science (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to preparation technologies of a chemical product, and particularly to preparation technologies of double-acid-single-alcohol copolymerization modification PET-A and a unidirectional heat shrinkable film thereof. A preparation method of the double-acid-single-alcohol copolymerization modification PET-A comprises adopting pure terephthalic acid (PTA), isophtalic acid (IPA), and mono ethylene glycol (MEG) as main raw materials and acquiring PET-A by carrying out ternary polymerization modification on the raw materials. The preparation technologies of the unidirectional heat shrinkable film of the double-acid-single-alcohol copolymerization modification PET-A comprises two types of preparation technologies, and one is vertical and the other is horizontal. Heat shrinkable films prepared by adopting the two types of preparation technologies have the same performance. The preparation technologies of the invention have the advantages of easy availability of raw materials, simple and environmental protecting preparation technology, high transparency of products, and broad applications. The preparation technologies of the unidirectional heat shrinkable film provided by the invention are specially used for preparing food packaging heat shrinkable film materials. Finished products obtained by drawing the products vertically or horizontally have good transparency and heat shrinkage rate of the finished products reaches 45-80% within 2-3s at a temperature of 95-130DEG C. The unidirectional heat shrinkable film of the invention can replace poisonous PVC heat shrinkable food packaging bags and other series of heat shrinkable packaging materials.
Description
Technical field
The present invention relates to a kind of preparation technology of Chemicals, particularly the pure modification by copolymerization PET-A of a kind of bisgallic acid one and unidirectional heat shrink film preparation technology thereof.
Background technology
Polyester (PET) heat-shrinkable film is a kind of Novel hot shrink wrap material, it have be easy to reclaim, the characteristics of nontoxic, tasteless, satisfactory mechanical property and environmental protection.In most developed countries, the PETG heat-shrinkable film has become the ideal substitute that replaces polyvinyl chloride (PVC) heat-shrinkable film; China will have carried out the State Council's file about forbidding PVC packaging material for food the end of the year in 2011.
At present, more than 100 of the domestic big-and-middle-sized production line of having introduced the PET biaxial stretching film, yearly capacity is about 1,500,000 tons, this product is the nonpolar rigid macromolecule material of a kind of crystallinity, its stretched film adopts the thin neck drawing process of bidirectional high speed high temperature crystallization in length and breadth, be specially that extension width is to the bidirectional balanced film of face gradually from starting, this kind film has in the lower non-shrinking characteristics of high temperature (150 ℃).Common PET is that its film is processed and can only be obtained at 150 ℃ through special process by the synthetic crystal type superpolymer of acid one alcohol, in 5min, and the percent thermal shrinkage below 30%, result of study shows, if will obtain the PET film of high percent thermal shrinkage, must carry out modification.U.S. Yi Siman (EASFMAN) and Korea S SK company adopt glycol (ethylene glycol MEG and 1-4 cyclohexanedimethanol CHDM) sour modification by copolymerization to obtain the PETG heat-shrinkage material, its thermal contraction performance is good, but expensive, and CHDM easily produces objectionable impurities methyl alcohol in reaction process.Sign in this, seek starting material and be easy to get, preparation technology is simple, cheap, and broad-spectrum heat-shrinkage material is imperative.
Summary of the invention
The technical problem to be solved in the present invention is: provide that a kind of starting material are easy to get, preparation technology is simple, product transparency high, broad-spectrum environment-friendly PE T-A material and a kind of drawing process is simple, percent thermal shrinkage is high, properties is excellent unilateral stretching heat-shrinkable film.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of a kind of bisgallic acid one pure modification by copolymerization PET-A, take pure terephthalic acid (PTA), m-phthalic acid (IPA) and ethylene glycol (MEG) makes the PET-A polyester as main raw material carries out the terpolymer modification, and concrete preparation process is as follows:
(1) preliminary polymerization is prepared raw material PTA, IPA, MEG, antimonous oxide, magnesium acetate, manganese acetate, triphenyl phosphite and triphenylphosphate, and wherein following proportioning is in molar ratio:
PTA:IPA=（0.65～0.88）:（0.12～0.35）；
（PTA+IPA）：MEG=1:（1.25～1.75）；
Following proportioning is in mass ratio:
(PTA+IPA): antimonous oxide: magnesium acetate: manganese acetate=
1:(0.03～0.05)%:(0.035～0.05)%:(0.02～0.03)%；
(PTA+IPA): triphenyl phosphite: triphenylphosphate=1:0.02%:0.01%;
Ready material is dropped into to the slurries that in the making beating still, making beating 0.5h must mix according to the order of MEG, PTA, IPA, antimonous oxide, magnesium acetate, manganese acetate, triphenyl phosphite and triphenylphosphate, then slurries are pressed in esterifying kettle and heat up and carry out esterification, temperature is controlled at 190～250 ℃, esterifying kettle still top temperature is controlled at below 95～110 ℃, normal pressure esterification reaction 200～300min; With the 1molPTA esterification, obtain 2molH
2O calculates the theoretical aquifer yield of this esterification, when the esterifying kettle still eject the water yield reach theoretical aquifer yield 95% the time, stopped reaction;
(2) further polymerization is pressed into polymerization reactor by the slurries after above-mentioned esterification end, and temperature is controlled at 275～280 ℃, and vacuum degree control is at 0.1MPa, reaction times is 150～300min, when product property viscosity is 0.68～0.85, when fusing point is 160～235 ℃, stopped reaction;
(3) the finished product packing PET-A polyester fondant that above-mentioned further polymerization obtains is cooling, pelletizing, check, the end product packing.
Described PTA:IPA=(0.65～0.88): when (0.12～0.35), product property viscosity can be 0.68～0.85, fusing point is 160～235 ℃ of scopes, the mol ratio of above-mentioned PTA:IPA is key point of the present invention, percent thermal shrinkage is 45～75%, have thermalsealing bond strength, be applicable to the heat-shrinkable film of all trades and professions and the wrapping material of other purposes.
The esterifying kettle still of described step (1) eject the water yield reach theoretical aquifer yield 95% the time, still top temperature drops to below 65 ℃, temperature in the kettle rises to 260 ℃.
The product that described terpolymer modification makes is hypocrystalline or noncrystalline PET-A polyester.
The unidirectional heat shrink film preparation technology of a kind of PET-A, comprise two kinds of preparation technologies of vertical and horizontal heat-shrinkable film, and the properties of two kinds of preparation technology's gained heat-shrinkable film is identical, and wherein, vertically the preparation technology of heat-shrinkable film has following steps:
(1) dried PETA polyester raw material added to melting in twin screw extruder, extrude, Cast Strip, cooling, moulding, the twin screw extruder temperature is controlled at 120～255 ℃, while extruding Cast Strip, die head temperature is controlled at 230～255 ℃, uses Cast Strip roller and cold wind lower than 30 ℃ to carry out cooling to Cast Strip;
(2) Cast Strip being sent into to the far infrared drawing zone, is 65～120 ℃ at draft temperature, and draw ratio is that longitudinal stretching is carried out to Cast Strip in 1:3.5～4.5 o'clock, by the temperature of 65～100 ℃, film is heat-treated after longitudinal stretching;
(3) above-mentioned form film is cooling in air, then rolling, check, end product packing.
A kind of preparation technology of horizontal heat-shrinkable film has following steps:
(1) dried PET-A polyester raw material added to melting in twin screw extruder, extrude, Cast Strip, cooling, moulding, the twin screw extruder temperature is controlled at 120～255 ℃, while extruding Cast Strip, die head temperature is controlled at 230～255 ℃, uses Cast Strip roller and cold wind lower than 30 ℃ to carry out cooling to Cast Strip;
(2) preheating section of Cast Strip being sent into to the cross directional stretch unit carries out preheating with 75～90 ℃, at draft temperature, is then 65～120 ℃, and draw ratio is that cross directional stretch is carried out in 1:3.5～4.5 o'clock, then by the temperature of 65～100 ℃, film is heat-treated;
(3) above-mentioned in type film is cooling in air, then rolling, check, end product packing.
The present invention adopts the pure modification by copolymerization PET-A polyester of bisgallic acid one, and starting material are easy to get, the simple environmental protection of preparation technology, the product transparency is high, processing characteristics is excellent, can be widely used in extrude, the field such as blowing, injection moulding and curtain coating; The preparation technology of unidirectional heat shrink film of the present invention is exclusively used in food product pack heat-shrinkable film material, the finished product transparency of product after vertical or horizontal stretching is good, percent thermal shrinkage reaches 45～80%, alternative poisonous PVC thermal contraction food pack and other serial heat shrinkable package materials in 95～130 ℃, 2～3s.
The accompanying drawing explanation
The present invention is further described below in conjunction with drawings and Examples;
Fig. 1 is preparation technology's schematic diagram of vertical heat-shrinkable film of the present invention;
Fig. 2 is preparation technology's schematic diagram of horizontal heat-shrinkable film of the present invention;
1. extrude district, 2. Cast Strip district, 3. far infrared drawing zone, 4. heat-treatment zone, 5. rolling, 6. preheating section, 7. drawing zone.
Embodiment
Example one
The preparation method of a kind of bisgallic acid one pure modification by copolymerization PETA, take pure terephthalic acid (PTA), m-phthalic acid (IPA) and ethylene glycol (MEG) to make the PET-A polyester as main raw material carries out the terpolymer modification, and the concrete technology step is as follows:
(1) preliminary polymerization is prepared raw material PTA 6kg, IPA 1.38kg, MEG 3.8kg, antimonous oxide 3.5g, magnesium acetate 2.6g, manganese acetate 2.0g, triphenyl phosphite 1.47g and triphenylphosphate 0.38g;
By the addition sequence of ready material according to MEG, PTA, IPA, antimonous oxide, magnesium acetate, manganese acetate, triphenyl phosphite and triphenylphosphate, drop into the slurries that in the making beating still, making beating 0.5h must mix, then slurries are pressed in esterifying kettle and heat up and carry out esterification, temperature is controlled at 190～250 ℃, esterifying kettle still top temperature is controlled at below 95～110 ℃, normal pressure esterification reaction 200～300min; With the 1molPTA esterification, obtain 2molH
2O calculates this esterification and obtains theoretical aquifer yield, when the esterifying kettle still eject the water yield reach theoretical aquifer yield 95% the time, stopped reaction;
(2) further polymerization is pressed into polymerization reactor by the slurries after above-mentioned esterification end, and temperature is controlled at 275～280 ℃, and vacuum degree control is at 0.1MPa, reaction times is 150～300min, when product property viscosity is 0.68～0.85, when fusing point is 210～235 ℃, stopped reaction;
(3) the finished product packing PETA polyester fondant that above-mentioned further polymerization obtains is cooling, pelletizing, check, the end product packing.
The percent thermal shrinkage of the present embodiment gained finished product is 45～60%.
Example two
The preparation method of a kind of bisgallic acid one pure modification by copolymerization PET-A, take pure terephthalic acid (PTA), m-phthalic acid (IPA) and ethylene glycol (MEG) to make the PET-A polyester as main raw material carries out the terpolymer modification, and the concrete technology step is as follows:
(1) preliminary polymerization is prepared raw material PTA 6kg, IPA 3.9kg, MEG 6.1kg, antimonous oxide 3.5g, magnesium acetate 3.5g, manganese acetate 2g, triphenyl phosphite 1.8g and triphenylphosphate 1g;
By the addition sequence of ready material according to MEG, PTA, IPA, antimonous oxide, magnesium acetate, manganese acetate, triphenyl phosphite and triphenylphosphate, drop into the slurries that in the making beating still, making beating 0.5h must mix, then slurries are pressed in esterifying kettle and heat up and carry out esterification, temperature is controlled at 190～250 ℃, esterifying kettle still top temperature is controlled at below 95～110 ℃, normal pressure esterification reaction 200～300min; With the 1molPTA esterification, obtain 2molH
2O calculates this esterification and obtains theoretical aquifer yield, when the esterifying kettle still eject the water yield reach theoretical aquifer yield 95% the time, stopped reaction;
(2) further polymerization is pressed into polymerization reactor by the slurries after above-mentioned esterification end, and temperature is controlled at 275～280 ℃, and vacuum degree control is at 0.1MPa, reaction times is 150～300min, when product property viscosity is 0.68～0.85, when fusing point is 170～185 ℃, stopped reaction;
(3) the finished product packing PET-A polyester fondant that above-mentioned further polymerization obtains is cooling, pelletizing, check, the end product packing.
The percent thermal shrinkage of the present embodiment gained finished product is 65～80%.
Example three
By above-mentioned example one and the standby a kind of vertical heat-shrinkable film of example two gained PET-A polyester, its preparation technology has following steps:
(1) dried PET-A polyester raw material added to melting in twin screw extruder, extrude, Cast Strip, cooling, moulding, extrude 1st one district, district to 190 ℃ respectively of the temperature in 5th district, 220 ℃, 245 ℃, 255 ℃, 255 ℃, extrude Cast Strip district 2 six district's die head temperatures and be controlled at respectively 245 ℃, 245 ℃, 255 ℃, 255 ℃, 245 ℃, 245 ℃, use Cast Strip roller and cold wind lower than 30 ℃ to carry out cooling to Cast Strip;
(2) Cast Strip being sent into to far infrared drawing zone 3, is 85～90 ℃ at draft temperature, when draw ratio is 1:4, longitudinal stretching is carried out in Cast Strip, after longitudinal stretching, 4 use five district's temperature are respectively 65 ℃ in heat-treatment zone, and 70 ℃, 70 ℃, 70 ℃, the temperature of 65 ℃ is heat-treated film;
(3) above-mentioned form film is cooling in air, then rolling 5, check, end product packing.
Example four
By above-mentioned example one and the standby a kind of horizontal heat-shrinkable film of example two gained PET-A polyester, its preparation technology has following steps:
(1) dried PET-A polyester raw material added to melting in twin screw extruder, extrude, Cast Strip, cooling, moulding, forcing machine one district is to 190 ℃ respectively of the temperature in 5th district, 220 ℃, 245 ℃, 255 ℃, 255 ℃, while extruding Cast Strip, six district's die head temperatures are controlled at respectively 245 ℃, 245 ℃, 255 ℃, 255 ℃, 245 ℃, 245 ℃, use Cast Strip roller and cold wind lower than 30 ℃ to carry out cooling to Cast Strip;
(2) preheating section 6 four district's temperature of Cast Strip being sent into to the cross directional stretch unit are respectively 90 ℃, and 75 ℃, 80 ℃, 80 ℃ are carried out preheating, then in drawing zone 7 four district's temperature, be respectively 80 ℃, 85 ℃, 90 ℃, 90 ℃ stretch, when draw ratio is 1:4, carry out cross directional stretch, reusable heat treatment zone 4 four district's temperature are 85 ℃, 90 ℃, 90 ℃, 90 ℃ film is heat-treated;
(3) above-mentioned in type film is cooling in air, then rolling, check, end product packing.The correlated performance of above-mentioned example four gained heat-shrinkable film is as shown in the table:
As seen from the above table, the finished product transmittance of the present embodiment gained PET-A polyester after vertical or horizontal stretching is good, and percent thermal shrinkage reaches 73%, alternative poisonous PVC thermal contraction food pack and other serial heat shrinkable package materials in 100 ℃, 2-3s.
Claims (5)
1. the preparation method of bisgallic acid one a pure modification by copolymerization PET-A is characterized in that: concrete preparation process is as follows:
(1) preliminary polymerization is prepared raw material PTA, IPA, MEG, antimonous oxide, magnesium acetate, manganese acetate, triphenyl phosphite and triphenylphosphate, and wherein following proportioning is in molar ratio:
PTA:IPA=（0.65～0.88）:（0.12～0.35）；
（PTA+IPA）：MEG=1:（1.25～1.75）；
Following proportioning is in mass ratio:
(PTA+IPA): antimonous oxide: magnesium acetate: manganese acetate=
1:(0.03～0.05)%:(0.035～0.05)%:(0.02～0.03)%；
(PTA+IPA): triphenyl phosphite: triphenylphosphate=1:0.02%:0.01%;
Ready material is dropped into to the slurries that in the making beating still, making beating 0.5h must mix according to the order of MEG, PTA, IPA, antimonous oxide, magnesium acetate, manganese acetate, triphenyl phosphite and triphenylphosphate, then slurries are pressed in esterifying kettle and heat up and carry out esterification, temperature is controlled at 190～250 ℃, esterifying kettle still top temperature is controlled at below 95～110 ℃, normal pressure esterification reaction 200～300min; With the 1molPTA esterification, obtain 2molH
2O calculates the theoretical aquifer yield of this esterification, when the esterifying kettle still eject the water yield reach theoretical aquifer yield 95% the time, stopped reaction;
(2) further polymerization is pressed into polymerization reactor by the slurries after above-mentioned esterification end, temperature is controlled at 275～280 ℃, vacuum degree control is at 0.1MPa, reaction times is 150～300min, according to limiting viscosity 0.68～0.85 and the fusing point of customer need, be to control in 160～235 ℃ of scopes, stopped reaction;
(3) the finished product packing PET-A polyester fondant that above-mentioned further polymerization obtains is cooling, pelletizing, check, the end product packing;
Described PTA:IPA=(0.65～0.88): when (0.12～0.35), product property viscosity can be 0.68～0.85, fusing point is 160～235 ℃ of scopes, according to claim, the mol ratio of above-mentioned PTA:IPA is key point, percent thermal shrinkage is 45～75%, has thermalsealing bond strength, is applicable to the heat-shrinkable film of all trades and professions and the wrapping material of other purposes.
2. the preparation method of bisgallic acid one pure modification by copolymerization PET-A as claimed in claim 1, it is characterized in that: the esterifying kettle still in described step (1) eject the water yield reach theoretical aquifer yield 95% the time, still top temperature drops to below 65 ℃, and temperature in the kettle rises to 260 ℃.
3. the preparation method of bisgallic acid one pure modification by copolymerization PET-A as claimed in claim 1, it is characterized in that: the finished product in described step (3) is hypocrystalline or noncrystalline PET-A polyester.
4. the preparation method of bisgallic acid one pure modification by copolymerization PET-A as claimed in claim 1, it is characterized in that: the preparation technology of a kind of vertical heat-shrinkable film of this PET-A has following steps:
(1) dried PET-A polyester raw material added to melting in twin screw extruder, extrude, Cast Strip, cooling, moulding, the twin screw extruder temperature is controlled at 120～255 ℃, while extruding Cast Strip, die head temperature is controlled at 230～255 ℃, uses Cast Strip roller and cold wind lower than 30 ℃ to carry out cooling to Cast Strip;
(2) Cast Strip being sent into to the far infrared drawing zone, is 65～120 ℃ at draft temperature, and draw ratio is that longitudinal stretching is carried out to Cast Strip in 1:3.5～4.5 o'clock, by the temperature of 65～100 ℃, film is heat-treated after longitudinal stretching;
(3) above-mentioned form film is cooling in air, then rolling, check, end product packing.
5. the preparation method of bisgallic acid one pure modification by copolymerization PET-A as claimed in claim 1, it is characterized in that: the preparation technology of a kind of horizontal heat-shrinkable film of this PET-A has following steps:
(1) dried PET-A polyester raw material added to melting in twin screw extruder, extrude, Cast Strip, cooling, moulding, the twin screw extruder temperature is controlled at 120～255 ℃, while extruding Cast Strip, die head temperature is controlled at 230～255 ℃, uses Cast Strip roller and cold wind lower than 30 ℃ to carry out cooling to Cast Strip;
(2) preheating section of Cast Strip being sent into to the cross directional stretch unit carries out preheating with 75～90 ℃, at draft temperature, is then 65～120 ℃, and draw ratio is that cross directional stretch is carried out in 1:3.5～4.5 o'clock, then by the temperature of 65～100 ℃, film is heat-treated;
(3) above-mentioned in type film is cooling in air, then rolling, check, end product packing.
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| CN109776771A (en) * | 2019-01-10 | 2019-05-21 | 山东中塑泰富科技有限公司 | A kind of Heat Shrinkage Film Polyester slice and preparation method thereof |
| CN110423442A (en) * | 2019-08-12 | 2019-11-08 | 宜兴西工维新科技有限公司 | A kind of degradable composite membrane and preparation method thereof |
| CN115725059B (en) * | 2021-08-31 | 2024-02-23 | 华润化学材料科技股份有限公司 | Copolyester material and preparation method and application thereof |
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